Method and apparatus for fabricating a thin-film solar cell utlizing a hot wire chemical vapor

ABSTRACT

A thin-film solar cell is provided. The thin-film solar cell comprises an a-SiGe:H (1.6eV) n-i-p solar cell having a deposition rate of at least ten (10) Å/second for the a-SiGe:H intrinsic layer by hot wire chemical vapor deposition. A method for fabricating a thin film solar cell is also provided. The method comprises depositing a n-i-p layer at a deposition rate of at least ten (10) Å/second for the a-SiGe:H intrinsic layer.

CONTRACTUAL ORIGIN OF THE INVENTION

[0001] The United States Government has rights in this invention under Contract No. DE-AC36-99GO10337 between the United States Department of Energy and the National Renewable Energy Laboratory, a division of the Midwest Research Institute.

TECHNICAL FIELD

[0002] This invention relates generally to a thin-film solar cell and, more particularly, it relates to an apparatus and process to fabricate an a-SiGe:H 1.6 eV optical gap n-i-p solar cell at a deposition rate of ten (10) Å/s for the a-SiGe:H intrinsic layer using hydrogen dilution by the hot-wire chemical vapor deposition (CVD) technique.

BACKGROUND ART

[0003] With concerns about rising fuel costs, energy security, statewide brownouts, and demand surges that exceed electrical supply, solar electric systems are needed to meet a greater share of energy needs. Photovoltaic devices, i.e., solar cells, are capable of converting solar radiation into usable electrical energy. The energy conversion occurs as the result of what is known as the photovoltaic effect. Solar radiation impinging on a solar cell and absorbed by an active region of semiconductor material generates electricity.

[0004] In recent years, technologies relating to thin-film solar cells have been advanced to realize inexpensive and lightweight solar cells and, therefore, thinner solar cells manufactured with less material have been demanded. This is especially true in the space industry with the solar cells powering satellites and other space vehicles.

[0005] The current state of the art in solar cell design is to deposit a photoactive material onto a substrate. Hydrogenated amorphous silicon-germanium (a-SiGe:H) alloy accounts for over half the materials in most commercial multi-junction amorphous silicon thin film solar cells. a-SiGe:H has been used in the tandem and triple-junction solar cells to improve the red response. However, a-SiGe:H alloy has poorer electronic properties than a-Si:H because of higher defect densities, weaker hydrogen bonds and other structural defects. This problem is more pronounced for low bandgap a-SiGe:H alloy with Ge content greater than 50%. In addition, the cost of germane gas is high.

[0006] Various techniques have been tried to improve the property of the a-SiGe:H alloy. Growing a-SiGe:H alloy near the threshold of microcrystallinity using hydrogen dilution at low deposition rate (˜1 Å/s) by rf plasma-enhanced CVD (PECVD) and applied graded alloy layers were two of many techniques that have significantly improved a-SiGe:H solar cell performance. Despite the recent development of a microcrystalline silicon (μc-Si) solar cell and its potential of replacing a-SiGe:H materials, a-SiGe:H solar cell exhibits higher open circuit voltage (V_(oc)), a tunable bandgap, and potential for further improvement. With these considerations, a-SiGe:H alloys are still considered as promising materials for use in commercial a-Si:H based solar cells fabrications.

[0007] Deposition rate is one of the important factors to increase the throughput and reduce the capital cost for PV production. The deposition rate of the photoactive material onto the substrate has been, typically, approximately one (1) Å/second or less with a typical ten (10%) percent stable efficiency for a-Si:H solar cells. It is even more crucial for a-SiGe:H because of the large amount of materials used in the solar cells. The best a-Si:H based solar cells are made at the deposition rate about 1 Å/s. Up to date, the properties of the high deposition rate (greater than 1 Å/s) materials remain inferior to the one at 1 Å/s. The efficiency of the high rate solar cells, as a consequence, is lower than the ones at 1 Å/s.

[0008] Accordingly, the time to manufacture the solar cell increases the cost of manufacture thereby increasing the cost to the ultimate user. In the very near future, to further increase the volume of production of solar cells to meet the high demand, an efficient high deposition rate will be required.

[0009] Accordingly, there exists a need for a thin-film solar cell fabricated with a high deposition rate. Additionally, a need exists for a thin-film solar cell with a high deposition rate and increased efficiency. Furthermore, there exists a need for a thin-film solar cell fabricated with a high deposition rate utilizing a hot wire chemical vapor deposition technique with optimum parameters to achieve efficient high deposition rates of approximately ten (10) Å/second.

DISCLOSURE OF INVENTION

[0010] The present invention is a thin-film solar cell. The thin-film solar cell comprises an a-SiGe:H (1.6 eV) n-i-p solar cell having a deposition rate of at least ten (10) Å/second for the a-SiGe:H intrinsic layer by a hot wire chemical vapor deposition technique.

[0011] The present invention additionally includes a method for fabricating a thin film solar cell. The method comprises depositing an n-i-p layer at a deposition rate of at least ten (10) Å/second for the a-SiGe:H intrinsic layer.

[0012] The present invention further includes means for depositing an a-SiGe:H intrinsic layer at a deposition rate of at least ten (10) Å/second.

BRIEF DESCRIPTION OF DRAWINGS

[0013] The accompanying drawings, which are incorporated in and form a part of the specification, illustrate the preferred embodiments of the present invention, and together with the descriptions serve to explain the principles of the invention.

[0014]FIG. 1 is a top schematic view of a T-system for fabricating a thin film solar cell utilizing a hot wire chemical vapor deposition technique, constructed in accordance with the present invention;

[0015]FIG. 2 is an exploded view of the n/p chamber and the i-chamber of the T-system of FIG. 1 for fabricating the thin film solar cell utilizing a hot wire chemical vapor deposition technique, constructed in accordance with the present invention;

[0016]FIG. 3 is a sectional view of the thin film solar cell utilizing a hot wire chemical vapor deposition technique of FIG. 1, constructed in accordance with the present invention;

[0017]FIG. 4 is a table of the variables in the optimization process of the present invention;

[0018]FIG. 5 is a table of the best parameters of the process of the present invention with the i-layer having three layers, namely, the first layer, the second layer, and the third layer; and

[0019]FIG. 6 is schematic view of the graded a-SiGe:H i-layer in the solar cell, constructed in accordance with the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0020] As illustrated in FIG. 1, the present invention is a process to fabricate a high deposition rate a-SiGe:H (1.6 eV) n-i-p solar cell 10 (as illustrated in FIG. 3) at a deposition rate of approximately ten (10) Å/second for the a-SiGe:H intrinsic layer using hydrogen dilution by the hot-wire chemical vapor deposition technique (as illustrated in FIG. 1). The inventors of the present application have found the optimal process parameters for constructing the a-SiGe:H (1.6 eV) n-i-p solar cell 10 that significantly reduces cost and increase throughput for a-Si solar cells 10.

[0021] The inventors of the invention of the present application have found that in constructing the a-SiGe:H (1.6 eV) n-i-p solar cell 10, the maximum power (P_(max)) after 530 nm cut-off filter has been above four (4) mW/cm². This means that the solar cell 10 will contribute more than four (4%) percent efficiency in the tandem or triple junction a-Si:H solar cell 10. With conventional solar cells, the best P_(max) after 530 nm cut-off filter of a-SiGe:H solar cell is just over five (5) mW/cm₂ at one (1) Å/second, and about four (4) mW/cm² for three (3) and six (6) Å/second. The solar cell 10 of the present invention offers significant improvement over conventional solar cells in deposition rate and efficiency thereby reducing the costs in construction of the solar cell 10.

[0022] In this two-chamber load-locked system 14, one chamber (i-chamber) 18 is only used to grow the a-SiGe:H intrinsic layer; the other chamber (dopant chamber) 16 is used to grow doped layers. As shown in FIG. 2, a spiral tungsten (W) wire 22 with a diameter of approximately 0.5 mm is positioned approximately 5 cm below the heated substrate. A heater 30 can be mounted to or placed in contact with the substrate 26. The tungsten filament 22 is heated to about 2100° C. by using an AC current. A process gas 20 preferably consisting of SiH₄, GeH₄, and H₂ passes by the hot filament 22, dissociates, and leads to Si/Ge/H deposition on the substrate 26. With the aid of a load-lock system 14 (see FIG. 1), the substrate 26 can be transported between two chambers 16 and 18 and minimizing the cross contamination in solar cell fabrication.

[0023] As illustrated in FIG. 3, the single junction solar cell 10 of the present invention has a structure of gl/TCO/p-i-n/Ag or SS/Ag/n-i-p/TCO. The TCO layer 26 is a transparent conducting oxide layer comprising, for instance, ZnO, indium tin oxide (ITO), or SnO₂. Tandem and triple-junction solar cells 10 are also within the scope of the present invention by adding additional p-i-n layers 28 or n-i-p layers 28, respectively.

[0024] The Ge concentration in the film, substrate temperature, hydrogen dilution, multi-step i-layer, chamber pressure, and deposition time has been varied in the optimization process to focus on achieving the ten (10) Å/second deposition rate a-SiGe:H. The inventors of the present application have discovered that the hydrogen dilution and multi-step i-layer are the key variables that lead to improve the solar cell 10 efficiency. For the a-SiGe:H i-layer materials with a deposition rate greater than ten (10) Å/second, multiple filaments, higher SiH₄ flow rate, higher pressure, and higher filament current will be used.

[0025]FIG. 4, table 1, lists the variables in the optimization process. FIG. 5, table 2, illustrates the best parameters of the process. As illustrated therein, the i-layer has three layers, namely, the first layer, the second layer, and the third layer. FIG. 6 illustrates the graded a-SiGe:H i-layer of the solar cell 10.

[0026] The optimum deposition parameters for the n-layer, the i-layer, and the p-layer are as follows: T_(sub) (° C.): 250 SiH₄ flow rate (sccm): 25 5% H₂ PH3 flow rate (sccm): 5 Pressure (mT): 12 Deposition time (sec): 60 Filament current (A): 16

[0027] n-layer:

[0028] i-layer:

[0029] See Table 2.

[0030] p-layer: T_(sub) (° C.): 170 SiH₄ flow rate (sccm): 3 H₂ flow rate (sccm): 100 TMB flow rate (sccm): 6 Pressure (mT): 70 Deposition time (sec): 50 Filament current (A): 16

[0031] With the solar cell 10 of the present invention utilizing the above parameters, the best cell performance after 530 nm cut-off filter is V_(oc)=0.770 V, FF=0.677, J_(sc)=8.08 mA/cm², and P_(mzx)=4.21 mW/cm². This achieves an efficient high deposition rate solar cell with a deposition rate of approximately ten (10) Å/second.

[0032] In conclusion, the present invention is a high performance 1.6 eV solar cell 10 having an active layer deposited by hot wire chemical vapor deposition at a rate of ten (10) Å/s. A power output of 4.2 mW/cm₂ was measured through a 530 nm long pass filter. The double-junction solar cell 10 can exhibit an initial 11.7% and stable 9.6% active-area efficiency thereby allowing fabrication of high-efficiency amorphous silicon solar cells 10 at higher deposition rates, an important result for low-cost production of PV modules.

[0033] The foregoing exemplary descriptions and the illustrative preferred embodiments of the present invention have been explained in the drawings and described in detail, with varying modifications and alternative embodiments being taught. While the invention has been so shown, described and illustrated, it should be understood by those skilled in the art that equivalent changes in form and detail may be made therein without departing from the true spirit and scope of the invention, and that the scope of the present invention is to be limited only to the claims except as precluded by the prior art. Moreover, the invention as disclosed herein, may be suitably practiced in the absence of the specific elements which are disclosed herein. 

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
 1. A thin film solar cell, comprising: an n-type semiconductor layer; a p-type semiconductor layer; and two or more hydrogenated amorphous silicon-germanium (a-SiGe:H) intrinsic layers positioned between the n-type semiconductor layer and the p-type semiconductor layer.
 2. The thin film solar cell of claim 1, wherein the n-type semiconductor layer comprises hydrogenated amorphous silicon (a-Si:H).
 3. The thin film solar cell of claim 1, wherein the p-type semiconductor layer comprises hydrogenated amorphous silicon (a-Si:H).
 4. The thin film solar cell of claim 1, wherein the two or more a-SiGe:H intrinsic layers comprise three intrinsic layers.
 5. The thin film solar cell of claim 1, wherein the two or more a-SiGe:H intrinsic layers comprise three graded intrinsic layers.
 6. A method for fabricating a thin film solar cell, the method comprising: forming an n-type semiconductor layer; forming a p-type semiconductor layer; forming two or more hydrogenated amorphous silicon-germanium (a-SiGe:H) intrinsic layers between the n-type semiconductor layer and the p-type semiconductor layer.
 7. A method as defined in claim 6, wherein the two or more a-SiGe:H intrinsic layers are formed using hot wire chemical vapor deposition.
 8. A method as defined in claim 6, wherein the two or more a-SiGe:H intrinsic layers comprise three intrinsic layers formed using hot wire chemical vapor deposition.
 9. A method as defined in claim 6, wherein the two or more a-SiGe:H intrinsic layers are formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of from 30 to 50 sccm, H₂ flowed at a rate of from 0 to 190 sccm, and GeH₄ flowed at a rate of from 0 to 12.5 sccm.
 10. A method as defined in claim 6, wherein the two or more a-SiGe:H intrinsic layers are formed in chamber having pressure from 20 to 50 mT using hot wire chemical vapor deposition including SiH₄ flowed at a rate of from 30 to 50 sccm, H₂ flowed at a rate of from 0 to 190 sccm, and GeH₄ flowed at a rate of from 0 to 12.5 sccm.
 11. A method as defined in claim 6 wherein the two or more a-SiGe:H intrinsic layers comprise a first intrinsic layer, a second intrinsic layer, and a third intrinsic layer.
 12. A method as defined in claim 11 wherein the first intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm and H₂ flowed at a rate of approximately 150 sccm.
 13. A method as defined in claim 11 wherein the first intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 14. A method as defined in claim 11 wherein the first intrinsic layer is formed in a chamber having a pressure of approximately 42 pT using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 15. A method as defined in claim 11 wherein the second intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 4.3 sccm, and H₂ flowed at a rate of approximately 150 sccm.
 16. A method as defined in claim 11 wherein the second intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 4.3 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 17. A method as defined in claim 11 wherein the second intrinsic layer is formed in a chamber having a pressure of approximately 43 pT using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 4.3 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 18. A method as defined in claim 11 wherein the second intrinsic layer is has a Gallium to Silicon ratio (Ge/Si) of approximately 8%.
 19. A method as defined in claim 11 wherein the third intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 9.5 sccm, and H₂ flowed at a rate of approximately 150 sccm.
 20. A method as defined in claim 11 wherein the third intrinsic layer is formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 9.5 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 21. A method as defined in claim 11 wherein the third intrinsic layer is formed in a chamber having a pressure of approximately 45 pT using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm, GeH₄ flowed at a rate of approximately 9.5 sccm, H₂ flowed at a rate of approximately 150 sccm, and a deposition time of approximately 90 seconds.
 22. A method as defined in claim 11 wherein the third intrinsic layer is has a Gallium to Silicon ratio (Ge/Si) of approximately 16%.
 23. A method as defined in claim 11 wherein the first, second, and third intrinsic layers are formed using hot wire chemical vapor deposition including SiH₄ flowed at a rate of approximately 50 sccm and H₂ flowed at a rate of approximately 150 sccm.
 24. A method as defined in claim 23 wherein the second intrinsic layer has a Gallium to Silicon ratio (Ge/Si) of approximately 8%, and the third intrinsic layer has a Gallium to Silicon ratio (Ge/Si) of approximately 16%.
 25. A method as defined in claim 23 wherein the first intrinsic layer has a Gallium to Silicon ratio (Ge/Si) of approximately 0%, the second intrinsic layer has a Gallium to Silicon ratio (Ge/Si) of approximately 8%, and the third intrinsic layer has a Gallium to Silicon ratio (Ge/Si) of approximately 16%.
 26. A method as defined in claim 23 wherein the second intrinsic layer is formed using GeH₄ flowed at a rate of approximately 4.3 sccm.
 27. A method as defined in claim 23 wherein the third intrinsic layer is formed using GeH₄ flowed at a rate of approximately 9.5 sccm.
 28. A method as defined in claim 23 wherein the wherein the second intrinsic layer is formed using GeH₄ flowed at a rate of approximately 4.3 sccm and the third intrinsic layer is formed using GeH₄ flowed at a rate of approximately 9.5 sccm.
 29. A thin film solar cell deposition system, comprising: a chamber; and deposition means within the chamber for forming solar cell having an n-type semiconductor layer, a p-type semiconductor layer, and two or more hydrogenated amorphous silicon-germanium (a-SiGe:H) intrinsic layers between the n-type semiconductor layer and the p-type semiconductor layer.
 30. A thin film solar cell deposition system as defined in claim 29, wherein the deposition means forms the two or more a-SiGe:H intrinsic layer at a deposition rate of at least ten (10) Å/second.
 31. A thin film solar cell deposition system as defined in claim 29, wherein the deposition means comprises a hot wire chemical vapor deposition system.
 32. A thin film solar cell deposition system as defined in claim 31, wherein the solar cell is formed on a substrate and wherein the hot wire chemical vapor deposition system includes a tungsten filament having a temperature of approximately 2100° C.
 33. A thin film solar cell deposition system as defined in claim 32, wherein the tungsten filament is spaced approximately five centimeters from the substrate.
 34. A thin film solar cell deposition system as defined in claim 29, wherein the two or more a-SiGe:H intrinsic layers comprise three intrinsic layers.
 35. A thin film solar cell deposition system as defined in claim 29, wherein the three intrinsic layers each have a unique Gallium to Silicon ratio (Ge/Si).
 36. A thin film solar cell deposition system, comprising: means for forming a solar cell having an n-type semiconductor layer, a p-type semiconductor layer, and two or more hydrogenated amorphous silicon-germanium (a-SiGe:H) intrinsic layers between the n-type semiconductor layer and the p-type semiconductor layer at a rate of at least ten (10) Å/second.
 37. A thin film solar cell deposition system as defined in claim 36, wherein the means for forming the solar cell includes a hot wire chemical vapor deposition system. 